Denitrification in the river estuaries of the northern Baltic Sea

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.     

固态碳源去除地下水硝酸盐的模拟实验

选取了5种研究较少的固体材料,棉花、丝瓜络、甘蔗渣、可降解餐盒、木屑作为去除地下水硝酸盐的外加碳源。在锥形瓶中进行反硝化对比实验,研究了不同固态碳源下NO3--N、NO2--N、NH4+-N及pH的变化情况,分析了NO3--N及总氮的去除率。研究结果表明,反硝化过程中pH呈升高趋势,在6.9～8.5范围内浮动。可降解餐盒和丝瓜络相对于其他的固态碳源来说,对NO3--N和总氮有较高的去除率,但丝瓜络的总氮去除率明显低于可降解餐盒。可降解餐盒的硝酸盐去除率达到98.28%,总氮去除率达到93.48%。可降解餐盒能够有效地去除地下水硝酸盐,达到以废治废的效果,是经济有效的最佳固态碳源。     

Nitrous oxide generation in denitrifying phosphorus removal process: main causes and control measures

Despite the many benefits of denitrifying phosphorus removal process, the significant generation of nitrous oxide (N₂O), a potent greenhouse gas, remains a problem for this innovative and promising process. To better understand and more effectively control N₂O generation in denitrifying phosphorus removal process, batch experiments were carried out to investigate the main causes of N₂O generation, based on which the control measures were subsequently proposed. The results showed that N₂O generation accounted for 0.41 % of the total nitrogen removal in denitrifying phosphorus removal process, whereas, in contrast, almost no N₂O was generated in conventional denitrification process. It was further demonstrated that the weak competition of N₂O reductase for electrons and the high nitrite accumulation were the two main causes for N₂O generation, evidenced by N₂O production and reduction rates under different conditions. Accordingly, the reduction of N₂O generation was successfully achieved via two control measures: (1) the use of continuous nitrate addition reducing N₂O generation by around 91.4 % and (2) the use of propionate as the carbon source reducing N₂O generation by around 69.8 %.     

电化学脱硝过程参数的响应曲面优化研究

以Ti/IrO2-TiO2-RuO2为阳极,Cu/Zn合金电极为阴极,在无隔膜电解池中对这一新构造电极对的脱硝氮性能进行了研究。为了有效结合阴极硝氮还原能力和阳极氧化能力,采用响应曲面法中的Box-Behnken设计优化了对电化学脱硝过程有显著影响的4个重要因素:氯化钠含量、电流密度、pH和初始硝氮浓度。优化结果表明,相对于pH和初始硝氮浓度,氯化钠含量和电流密度对脱硝性能影响更大,而阴极硝氮还原性能主要受初始硝氮浓度、pH的影响。以6 h内电极对脱氮百分率为响应量,优化得最佳电化学脱硝过程参数为:氯化钠含量,1 g/L;电流密度,24.99 mA/cm2;pH,1.81;初始硝氮浓度100 mg/L。在此实验条件下,6 h内电极对脱氮百分率预测值为99.84%。通过3次重复验证实验,确认实际6 h内电极对脱氮百分率为91.34%。预测值与实测值两者相差不大,由此可知,Box-Behnken设计是一种优化电化学脱氮实验参数的有效方法,经过优化后的电极对具有较佳的脱氮效率。     

Nitrate removal under different ecological remediation measures in Taihu Lake: a 15 N mass-balance approach

Ecological remediation is an important measure for the protection of lake water quality in removing nutrients, such as nitrate (NO₃ ^?). In this study, four bioremediation processes (bare sediment, immobilized nitrogen cycling bacteria (INCB) added, Elodea nuttallii added, E. nuttallii-INCB assemblage) were operated at a lab to elucidate the effect of macrophyte appearance and INCB addition on NO₃ ^? removal and achieve the optimal processes for biomediation. ¹⁵?N-NO₃ solution was added to microcosms to identify the key nitrogen transformation processes responsible for NO₃ ^? removal. Results showed that nitrate removal was significantly enhanced after the addition of INCB and E. nuttallii. In the treatments with INCB added, E. nuttallii added, and INCB and E. nuttallii-INCB assemblage, nitrate removal ratio achieved 94.74, 98.76, and 99.15 %, respectively. In contrast, only 23.47 % added nitrate was removed in the control. Plant uptake and denitrification played an important role in nitrogen removal. The water quality was substantially improved by the addition of INCB and macrophyte that can accelerate denitrification and promote nitrogen assimilation of plants. The results indicated that plant uptake and microbial denitrification were key processes for nitrate removal.     

培养方式对废水脱氮与沼气脱硫污泥驯化影响

实验研究了底物、接种污泥和微生物生长方式对猪场废水脱氮和沼气脱硫耦联污泥驯化及活性恢复的影响,以解决快速富集培养废水脱氮与沼气脱硫微生物的问题。研究发现,就脱氮脱硫均达到60%的时间而言,接种厌氧污泥反应器为9 d,比接种好氧污泥反应器(18 d)和不接种污泥加填料反应器(21 d)更短。以含氮含硫废水为底物驯化时,接种厌氧污泥更有利于脱氮脱硫污泥的驯化;而同为接种好氧污泥时,以含氮含硫废水为底物的驯化方式更有利于脱氮脱硫污泥的驯化。污泥活性恢复实验中,以含氮废水+沼气(H2S)为底物培养驯化的污泥,硫转化活性恢复所用的时间为15 d,比含氮含硫废水为底物驯化污泥的活性恢复时间更长。     

Electrochemical wastewater treatment: influence of the type of carbon and of nitrogen on the organic load removal

Boron-doped diamond (BDD) and Ti/Pt/PbO₂ anodes were utilized to perform the electrodegradation of synthetic samples containing humic acid in the presence of different organic and inorganic carbon-containing and nitrogen-containing compounds. The influence of the chloride ion in the degradation process of the different synthetic samples was also assessed. The results showed that the anodic oxidation process can efficiently degrade recalcitrant compounds such as humic acid. The presence of carbonate in solution enhances the nitrogen removal, whereas it hinders the oxidation of the organic compounds. When organic nitrogen is present, it is converted to NH₄ ⁺, which in turn is oxidized to nitrate and to volatile nitrogen compounds. Hydroxyl radicals are more prone to oxidize the organic nitrogen than the ammonium nitrogen. The presence of chloride enhances the organic matter and nitrogen removal rates, BDD being the anode material that yields the highest removals.     

电化学法去除水中的硝酸根

以钛基氧化物涂层材料（Ti／SnO2-Sb2O5-IrO2）为阳极,碳纳米管修饰的石墨（GE—CNT）为阴极构建电化学系统进行硝酸根（NO3-）去除研究,考察了阴极材料、阴极电位和pH值对电化学法去除水中NO[的影响,同时检测了铵离子（NH4＋）和亚硝酸根（NO2-）的生成量。结果表明,利用碳纳米管修饰的石墨阴极可获得较好的硝态氮去除效果;随着阴极电位负移,NO3-去除率随之升高;酸性条件下NO3-去除率最高,NH;生成量也更多。对于由NO3-转化产生的NH4＋,在氯离子存在条件下再次进行电化学处理120min,其去除率可达97．1％。     

Direct measurement of denitrification activity in a Gulf coast freshwater marsh receiving diverted Mississippi River water

Wetland loss along the Louisiana Gulf coast and excessive nitrate loading into the Gulf of Mexico are interrelated environmental problems. Nitrate removal by soil denitrification activity was studied in a ponded freshwater marsh receiving diverted Mississippi River water for the purpose of reversing or slowing wetland loss. Labeled ¹⁵N-nitrate was applied at 3.8 g N m⁻² into four replicate study plots after removing above ground vegetation. Nitrogen gas (N₂) and nitrous oxide (N₂O) emissions from the plots were determined by isotope ratio mass spectrometry (IRMS). Nitrous oxide emissions were also compared with the results determined by gas chromatograph (GC). Results showed that it took 2 weeks to remove the added nitrate with N₂O emission occurring over a period of 4 d. The apparent denitrification dynamics were assumed to follow the Michaelis–Menten equation. The maximum denitrification rate and K_m value were determined as 12.6 mg N m ⁻² h⁻¹, and 6.5 mg N l⁻¹, respectively. Therefore the maximum capacity for nitrate removal by the marsh soil would be equivalent to 110 g N m⁻² yr⁻¹, with more than 30% of nitrogen gas evolved as N₂O. For typical nitrate concentrations in Mississippi River water of about 1 mg N l⁻¹, nitrate would be removed at a rate of 14.7 g N m⁻² yr⁻¹ with N₂O emission about 1.5%. A denitrification dynamic model showed that the efficiency of nitrate removal would largely depend on the water discharge rate into the ponded wetland. Higher discharge rate will result in less retention time for the water in the marsh where nitrate is denitrified.     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

Transformations,Lifetimes, and Sources of NO2, HONO,and HNO3 in Indoor Environments

Recent research has demonstrated that nitrogen oxides are transformed to nitrogen acids in indoor environments, and that significant concentrations of nitrous acid are present in indoor air. The purpose of the study reported in this paper has been to investigate the sources, chemical transformations and lifetimes of nitrogen oxides and nitrogen acids under the conditions existing in buildings. An unoccupied single family residence was instrumented for monitoring of NO, NO₂, NO_y, MONO, HNO₃, CO, temperature, relative humidity, and air exchange rate. For some experiments, NO₂ and HONO were injected into the house to determine their removal rates and lifetimes. Other experiments investigated the emissions and transformations of nitrogen species from unvented natural gas appliances. We determined that HONO is formed by both direct emissions from combustion processes and reaction of NO₂ with surfaces present indoors. Equilibrium considerations influence the relative contributions of these two sources to the indoor burden of HONO. We determined that the lifetimes of trace nitrogen species varied in the order NO ~ HONO > NO₂ >HNO₃. The lifetimes with respect to reactive processes are on the order of hours for NO and HONO, about an hour for NO₂, and 30 minutes or less for HNO3. The rapid removal of NO₂ and long lifetime of HONO suggest that HONO may represent a significant fraction of the oxidized nitrogen burden in indoor air.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.     

Nitrogen transformations and balance in constructed wetlands for slightly polluted river water treatment using different macrophytes

Nitrogen removal processing in different constructed wetlands treating different kinds of wastewater often varies, and the contribution to nitrogen removal by various pathways remains unclear. In this study, the seasonal nitrogen removal and transformations as well as nitrogen balance in wetland microcosms treating slightly polluted river water was investigated. The results showed that the average total nitrogen removal rates varied in different seasons. According to the mass balance approach, plant uptake removed 8.4–34.3 % of the total nitrogen input, while sediment storage and N₂O emission contributed 20.5–34.4 % and 0.6–1.9 % of nitrogen removal, respectively. However, the percentage of other nitrogen loss such as N₂ emission due to nitrification and denitrification was estimated to be 2.0–23.5 %. The results indicated that plant uptake and sediment storage were the key factors limiting nitrogen removal besides microbial processes in surface constructed wetland for treating slightly polluted river water.     

3株反硝化聚磷菌的分离与鉴定

通过烛缸法培养富集、分离,结合除磷试验、硝酸盐还原产气试验及异染颗粒和PHB颗粒染色辅助检验相结合的方法筛选,得到3株具有较高脱氮除磷效率的反硝化聚磷菌DNPA8, DNPA9和DNPA10。在富氮富磷培养基中培养48 h,各菌株的脱氮率均大于75%,除磷率均大于78%。采用多相分类的方法确定了3株反硝化聚磷菌的分类地位,DNPA8为嗜麦芽寡养单胞菌,DNPA9为水生丛毛单胞菌属首次发现的反硝化聚磷菌;DNPA10为约翰逊氏不动杆菌。该研究结果为富营养化水体的治理提供了有效的菌种资源。     

Searching efficient protection strategies for the eutrophied Gulf of Finland: the combined use of 1D and 3D modeling in assessing long-term state scenarios with high spatial resolution

An experiment combining the use of two ecosystem models was conducted to search for effective protection strategies for the Gulf of Finland (Baltic Sea). Reference and scenario simulations were first run with a one-dimensional (1D) model for seven main basins of the entire Baltic Sea until steady state was achieved. The obtained basinwise distributions of inorganic nitrogen (N) and phosphorus (P), as well as sediment labile P, were then used to initiate 5-y simulations with a three-dimensional (3D) ecosystem model. The results suggest that relatively small local load reductions (the "Finland" scenario) would improve only the state of adjacent coastal waters significantly. This would be the case, even for runs covering several decades, which clearly exceed the residence times of nutrients in the Gulf of Finland. A significant decrease from a substantial loading source to the Gulf (the "St. Petersburg" scenario) would decrease cyanobacterial biomasses in the entire Gulf of Finland and also immediately outside it. A reduction in the current Polish nutrient loads would improve the situation in the whole Baltic Proper and cause an extensive decline in cyanobacterial biomasses in the Gulf of Finland, as well. However, it would take several decades until the improvement caused by reducing loads in the "Poland" scenario is seen, while in the "St. Petersburg" scenario the corresponding time lag would only be a few years. Our results suggest that the common water protection policy in the Baltic Sea region should have the largest nutrient sources as its primary target, regardless of their location and country.     

Denitrification in cypress swamp within the Atchafalaya River Basin, Louisiana

Nitrogen has been implicated as a major cause of hypoxia in shallow water along the Louisiana/Texas, USA coasts. Excess nitrogen (mainly nitrate) from Mississippi and Atchafalaya River drainage basins may drive the onset and duration of hypoxia in the northern Gulf of Mexico. Restoring and enhancing denitrification have been proposed to reduce and control coastal hypoxia and improve water quality in the Mississippi River Basin. Sediments were collected from six baldcypress restoration sites within the Atchafalaya River Basin, Louisiana, USA. The acetylene blockage technique was used to measure background and potential sediment denitrification rates. Denitrification fluxes were measured before nitrate addition (background rates) and after nitrate addition of 100mgNl(-1) (potential denitrification) at three seasonal temperatures. Background denitrification was low across all cypress swamp sites ranging from 0.9 to 8.8, 0.6 to 28.5 and 8.8 to 47.5g N evolved ha(-1)d(-1) at water/sediment column temperatures of 8, 22 and 30 degrees C, respectively. After nitrate addition, temperature had a significant effect on sediment denitrification potential. Maximum rates measured at 8, 22 and 30 degrees C were approximately 250-260, 550 and 970gNha(-1)d(-1), respectively. Most of the added nitrate in water columns, incubated at 8 degrees C, was removed after 65d compared to 32d and 17d at 22 and 30 degrees C, respectively. These results indicate cypress swamps have the potential to assimilate and process elevated levels of floodwater nitrate with denitrification being a major removal mechanism.     

The impact of the 2005 Gulf hurricanes on pollution emissions as inferred from Ozone Monitoring Instrument (OMI) nitrogen dioxide

The impact of Hurricanes Katrina and Rita in 2005 on pollution emissions in the Gulf of Mexico region was investigated using tropospheric column amounts of nitrogen dioxide (NO₂) from the Ozone Monitoring Instrument (OMI) on the NASA Aura satellite. Around New Orleans and coastal Mississippi, we estimate that Katrina caused a 35% reduction in NO_x emissions on average in the three weeks after landfall. Hurricane Rita caused a significant reduction (20%) in NO_x emissions associated with power generation and intensive oil refining activities near the Texas/Louisiana border. We also found a 43% decrease by these two storms over the eastern Gulf of Mexico Outer Continental Shelf mainly due to the evacuation of and damage to platforms, rigs, and ports associated with oil and natural gas production.     

Use of carbon-based composites to enhance performance of TiO<Subscript>2</Subscript> for the simultaneous removal of nitrates and organics from aqueous environments

The simultaneous photocatalytic removal of nitrate from aqueous environment in presence of organic hole scavenger using TiO₂ has long been explored. However, the use of unmodified TiO₂ in such reaction resulted in non-performance or release of significant amount of undesirable reaction products in the process, a problem that triggered surface modification of TiO₂ for enhanced photocatalytic performance. Previous studies focused on decreasing rate of charge carrier recombination and absorption of light in the visible region. Yet, increasing active sites and adsorption capacity by combining TiO₂ with a high surface area adsorbent such as activated carbon (AC) remains unexploited. This study reports the potential of such modification in simultaneous removal of nitrates and oxalic acid in aqueous environment. The adsorptive behaviour of nitrate and oxalic acid on TiO₂ and TiO₂/AC composites were studied. The Langmuir adsorption coefficient for nitrate was four times greater than that of oxalic acid. However, the amount of oxalic acid adsorbed was about 10 times greater than the amount of nitrate taken up. Despite this advantage, the materials did not appear to produce more active photocatalysts for the simultaneous degradation of nitrate and oxalic acid. The photocatalytic activity of TiO₂ and its carbon-based composites was improved by combination with Cu₂O particles. Consequently, 2.5 Cu₂O/TiO₂ exhibited the maximum photocatalytic performance with 57.6 and 99.8% removal of nitrate and oxalic acid, respectively, while selectivity stood at 45.7, 12.4 and 41.9% for NH₄⁺, NO₂^? and N₂, respectively. For the carbon based, 2.5 Cu₂O/TiO₂-20AC showed removal of 12.7% nitrate and 80.3% oxalic acid and achieved 21.6, 0 and 78.4% selectivity for NH₄⁺, NO₂^? and N₂, respectively. Using the optimal AC loading (20 wt%) resulted in significant decrease in the selectivity for NH₄⁺ with no formation of NO₂^?, which unveils that selectivity for N₂ and low/no selectivity for undesirable products can be manipulated by controlling the rate of consumption of oxalic acid. In contract, no nitrate reduction was observed with Cu₂O promoted TiO₂-T and its TiO₂-(T)-20AC, which may be connected to amorphous nature of TiO₂-T and perhaps served as charge carrier trapping sites that impeded activity.     

SBR单级自养脱氮系统氮素转化途径

利用氮素计量关系和批式实验研究了SBR系统中基于短程硝化的单级自养脱氮特性和脱氮途径。结果表明,SBR系统获得良好脱氮效果,TN最高去除负荷和去除速率分别达0.49 kg N/(m3.d)和0.20 kg N/(kg VSS.d);系统中82%的氨氮转化成气体脱除,10%的氨氮转化成硝酸盐氮。批式实验结果表明,SBR系统中的污泥同时具有厌氧氨氧化、亚硝酸盐氧化和自养反硝化活性,三者的反应速率分别为0.12 kg NH4+-N/(kg VSS.d)、0.04 kg NO2--N/(kg VSS.d)和0.03 kg NO2--N/(kg VSS.d)。综上,SBR系统中氮的脱除是短程硝化、厌氧氨氧化和反硝化共同作用的结果,产生的硝酸盐是厌氧氨氧化和硝化作用所致。     

Gaseous Ammonia Uptake in Compost Biofilters as Related to Compost Water Content

Abstract

Sewage sludge and yard waste compost were used as biofilter materials and tested with respect to their capacity for removing ammonia from air at different water contents. Ammonia removal was measured in biofilters containing compost wetted to different moisture contents ranging from air dry to field capacity (maximum water holding capacity). Filters were operated for 15 days and subsequently analyzed for NH₃/NH₄ ⁺, NO₂ ^-, and NO₃ ^-. The measured nitrogen species concentration profiles inside the filters were used to calculate ammonia removal rates. The results showed that ammonia removal is strongly dependent on the water content in the filter material. At gravimetric water contents below 0.25 g H₂O g solids^-1 for the yard waste compost and 0.5 g H₂O g solids^-1 ammonia removal rates were very low but increased rapidly above these values. The sewage sludge compost filters yielded more than twice the ammonia removal rate observed for yard waste compost likely because of a high initial concentration of nitrifying bacteria originating from the wastewater treatment process and a high air-water interphase surface area that facilitates effective ammonia dissolution and transport to the biofilm.